Development of the ReaxFF Reactive Force Field for Describing Transition Metal Catalyzed Reactions, with Application to the Initial Stages of the Catalytic Formation of Carbon Nanotubes
Abstract
With the aim of developing a computationally inexpensive method for modeling the high-temperature reaction dynamics of transition metal catalyzed reactions we have developed a ReaxFF reactive force field in which the parameters are fitted to a substantial quantum mechanics (QM) training set, containing full reaction pathways for relevant reactions. In this paper we apply this approach to reactions involving carbon materials plus Co, Ni, and Cu atoms. We find that ReaxFF reproduces the QM reaction data with good accuracy while also reproducing the binding characteristics of Co, Ni, and Cu atoms to hydrocarbon fragments. To demonstrate the applicability of ReaxFF we performed high-temperature (1500 K) molecular dynamics simulations on a nonbranched all-carbon feedstock in the presence and absence of Co, Ni, and Cu atoms. We find that the presence of Co and Ni leads to substantial amounts of branched carbon atoms, leading eventually to the formation of carbon-nanotube-like species. In contrast, we find that under the same simulation conditions Cu leads to very little branching and leads to products with no nanotube character. In the absence of metals no branching is observed at all. These results suggest that Ni and Co catalyze the production of nanotube-like species whereas Cu does not. This is in excellent agreement with experimental observations, demonstrating that ReaxFF can provide a useful and computational tractable tool for studying the dynamics of transition metal catalytic chemistry.
Additional Information
© 2005 American Chemical Society. Received 19 August 2004. Published online 31 December 2004. Published in print 1 January 2005. K.D.N. thanks NSF-CSEM for a MURF-summer fellowship. This research was supported partially by NSF-NIRT and MARCO-FENA. The computation facilities of the MSC have been supported by grants from ARO-DURIP, ONR-DURIP, NSF (MRI, CHE), and IBM-SUR. In addition the MSC is supported by grants from DoE ASCI, ARO-MURI, ARO-DARPA, ONR-MURI, NIH, ONR, General Motors, ChevronTexaco, Seiko-Epson, Beckman Institute, and Asahi Kasei. We thank the reviewers for their useful comments on this manuscript.Attached Files
Supplemental Material - jp046244dsi20041110_072225.pdf
Supplemental Material - jp046244dsi20041110_072436.txt
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Additional details
- Eprint ID
- 77698
- DOI
- 10.1021/jp046244d
- Resolver ID
- CaltechAUTHORS:20170524-092030767
- Caltech Minorities Undergraduate Research Fellowship (MURF)
- NSF
- Microelectronics Advanced Research Corporation (MARCO)
- Army Research Office (ARO)
- Office of Naval Research (ONR)
- Center on Functional Engineered NanoArchitectonics (FENA)
- IBM
- Department of Energy (DOE)
- Defense Advanced Research Projects Agency (DARPA)
- NIH
- General Motors
- Chevron Texaco
- Seiko-Epson
- Caltech Beckman Institute
- Asahi Kasei
- Created
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2017-05-24Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field